The reactivity of 1,1-dialkoxyalkanes with niobium and tantalum pentahalides. Formation of coordination compounds, C–H and C–C bond activation and the X-ray structure of the stable carboxonium species [Me2CCHC(OMe)Me][NbCl5(OMe)]

Abstract

The reactions of the pentahalides NbX5 (X = Cl, Br) with the 1,1-dialkoxyalkanes CHR'(OEt)2 or 1,3-dioxolane yield the coordination adducts NbX5[kappa1-(OEt)CHR'(OEt)] (X = Cl, R' = H, 2a; X = Br, R' = H, 2b; X = Cl, R' = Me, 2c; X = Br, R' = Me, 2d) or NbCl5(kappa1-right angle OCH2OCH2C right angle H2), 3, respectively. Compounds 2a-c and 3 are stable at room temperature, while 2d slowly converts into the alkoxide NbBr4[OCH(Me)OEt], 4. Room-temperature fragmentations are observed upon reacting CH2(OMe)2, CHMe(OMe)2 and CMe2(OMe)2 with MX5 (M = Nb, Ta; X = Cl, Br). The complexes MX5[O(Me)(CH2X)], 5, and [MX3(OMe)2]2, 6, form selectively from MX5/CH2(OMe)2 (M = Nb, Ta; X = Cl, Br), while mixtures of [NbX4(OMe)]2 (X = Cl, 8a; X = Br, 8b) and organic halides are obtained from NbX5/CHMe(OMe)2. Instead, the reaction of NbCl5 with CMe2(OMe)2 affords the stable carboxonium species [Me2C=CHC(=OMe)Me][NbCl5(OMe)], 7, as prevalent product. Furthermore, 1,1-dialkoxyalkanes are generally activated by MF5 (M = Nb, Ta) at room temperature: according to the cases, alcohols, ethers, esters and ketones have been detected in the reaction mixtures after hydrolysis. In agreement with NMR data, the carboxonium ion [Me2C=CHC(=OMe)Me]+ is produced from NbF5/CMe2(OMe)2. The complexes NbF5[OEt(Me)], 9a, and NbF5[O=CH(OEt)], 9b, obtained by addition of CH2(OEt)2 to NbF5, have been characterised by NMR spectroscopy. Trimethyl formate, CH(OMe)3, reacts with NbX5 (X = Cl, Br) with formation of the alkoxides 6 and 8, in admixture with NbX5[O=CH(OMe)] and MeX; otherwise, MF5[O=CH(OMe)] and MF5(OMe2) have been synthesised from MF5/CH(OMe)3 (M = Nb, Ta). Complete screening of the organic fragments produced in the distinct reactions has been carried out by both GC-MS and NMR analyses on the reaction mixtures, after treatment with water. The solid state structures of the mixed halo-alkoxy complexes [TaX3(OMe)(mu-OMe)]2 (X = Cl, 6c; X = Br, 6d) and of the stable alkylated ketone containing species 7 have been ascertained by X-ray diffraction studies.

Reversible σ‐Dimerizations of Persistent Organic Radical Cations

“…[19,20] The C1ÀO2 single bond (1.428 (3) ) is consistent with carbon sp 3 hybridization, while the shorter C4 À O1 bond (1.265(4) ) has double-bond character, which was confirmed by IR spectroscopy (n C=O = 1595 cm À1 ). [21] Similar vibrational frequencies assigned to C=O partial double bonds were observed for [1-1] 2+ (1596 cm À1 ) and 2+ (1599 cm À1 ).…”

“…[4] However, it is shorter than the C À C bond distances (more than 1.7 ) in crowded hydrocarbons, which are stabilized by dispersion forces. [21] Similar vibrational frequencies assigned to C=O partial double bonds were observed for [1-1] 2+ (1596 cm À1 ) and 2+ (1599 cm À1 ). [21] Similar vibrational frequencies assigned to C=O partial double bonds were observed for [1-1] 2+ (1596 cm À1 ) and 2+ (1599 cm À1 ).…”

Alkyne-Induced Facile C–C Bond Formation of Two η2-Alkynes on Dinuclear Tantalum Bis(alkyne) Complexes To Give Dinuclear Tantalacyclopentadienes

“…The CC bond lengths (1.336(8) and 1.306(7) Å) of each alkyne coordinating to the tantalum atom are typical for the dianionic η 2 -alkyne ligands found for other tantalum alkyne complexes, , adopting a Ta­(V) metallacyclopropene canonical form. The bond lengths (2.080(4)–2.118(4) Å) of the Ta–O­(methoxy) bonds in a fragment of “Ta 2 (μ-OMe) 2 (μ-thf)” are similar to those of [TaCl 3 (OMe)] 2 (μ-OMe) 2 . The distance (3.3194(8) Å) between two tantalum centers is significantly longer than a typical Ta–Ta single-bond length (2.82–2.88 Å), suggesting no bonding interaction between the two tantalum centers.…”

Dimethyloxonium and Methoxy Derivatives of nido-Carborane and Metal Complexes Thereof

“…More detailed study of reactions of MX 5 (M = Nb, Ta; X = F, Cl) with acetals/ketals (1,1-dialkoxyalkanes) or trimethylformate revealed that the ethereal bonds can be broken by the MX 5 Lewis acids and the rate of the process is enhanced by the presence of the further vicinal ether function. The reaction pathway was found to include formation of the MX 5 (OMe 2 ) complexes, which were identified by NMR spectroscopy [24,25]. It prompted us to study reaction of nido-carborane with dimethoxymethane MeOCH 2 OMe in the presence of HgCl 2 .…”